Hetaryl-Substituted Phosphonium-Iodonium Ylides ... - ACS Publications

Jun 27, 2012 - Matveeva , E. D.; Podrugina , T. A.; Pavlova , A. S.; Mironov , A. V.; Borisenko , A. A.; Gleiter , R.; Zefirov , N. S. J. Org. Chem. 2...
3 downloads 0 Views 476KB Size
Download PDF
Article pubs.acs.org/joc

Hetaryl-Substituted Phosphonium-Iodonium Ylides in Synthesis of Heterocycles Elena D. Matveeva,*,†,‡ Tatyana A. Podrugina,† Marina A Taranova,† Anastasiya, M. Ivanova,† Rolf Gleiter,§ and Nikolay S. Zefirov†,‡ †

Department of Chemistry, Moscow State Lomonosov University, Russian Federation 119992, Moscow, Lenin Hills 1, Russia Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432, Chernogolovka, Moscow region, Russia § Organisch-Chemisches Institut der Universitaet Heidelberg, Im Neuenheimer Feld 270 D-69120 Heidelberg, Germany ‡

S Supporting Information *

ABSTRACT: A series of hitherto unknown hetaryl-substituted (in phosphonium part) phosphonium−iodonium ylides were synthesized. The reaction of these mixed phosphonium−iodonium ylides with acetylenes opens a way to new furyl annelated phosphinolines or unusually substituted phosphininofurans.

■

INTRODUCTION The work of Wittig et al., especially the discovery of carbonyl olefination by phosphonium ylides,1,2 has spurred the development of the chemistry of these species and other ylides.3,4 Some time ago, we focused our attention on mixed phosphonium− iodonium ylides, which reveal unusual reactivity. We have performed our studies mainly using carbonyl-stabilized mixed ylides 1, Ph3P(IPh)CHR (RCOOC2H5, COAr), which may be described by resonance structures 1a−d (Scheme 1).5,6

acetonitrile to 1 was studied by steady-state and time-resolved methods.11 It was found that the formation of the final products oxazole and phosphonium salt occurs in parallel processes starting by the heterolytic C−I+−Ph cleavage followed by a 1,3dipolar cycloaddition. The analogous reactions with a CC triple bond proceed quite differently. In analogy with the CN triple bond one anticipates the formation of the corresponding furans 3, which have been found experimentally.12 However, the main pathway found for this reaction was the formation of phosphinolines 4. In other words, interaction of acetylenes with ylides 1 using photochemical conditions led to a mixture of furans 3 and phosphinolines 4, their ratio being dependent on the nature of the substituents at the triple bond of acetylenes (Scheme 2).13,14 Previously, we proposed a mechanism (Scheme 3) for the formation λ5-phosphinolines and furans. Upon UV irradiation, the C−I bond is cleaved with the formation of an electrophilic intermediate, which interacts with the CC bond to give a carbocation B. Subsequent intramolecular electrophilic attack to the benzene ring attached to the phosphorus atom leads to the formation of six-membered phosphinoline12 (path b, Scheme 3). In other words, this mechanistic scheme includes electrophilic aromatic substitution as key mechanistic step. This idea was supported using the corresponding ylide, in which one phenyl substituent was replaced by a thiophene ring.14 In this case, the electrophilic substitution prefers the thiophene ring, known to be more inclined to undergo electrophilic

Scheme 1. Resonance Structures (a−d) of Ylide 1

Our previous research on the chemistry of such phosphonium−iodonium ylides revealed several different pathways for the reactions of these compounds, which crucially depend on the possibility of the conjugation shown. The resonance structure 1d clearly reveals the possibility for these ylides to play a role as nucleophile, having a negatively charged oxygen center. Indeed, we have shown that ylides 1 can be alkylated, silylated, or acetylated.7,8 Moreover, we have found that phosphonium−iodonium ylides enter into photochemical reaction of 1,3-dipolar cycloaddition (probably via intermediacy of transient 1.3-dipoles) with a triple CN bond to afford triphenylphosphonium-substituted oxazoles 2; their formation is obviously connected with a nucleophilic oxygen center of the ylides.9,10 The mechanism of the photoinduced cycloaddition of © XXXX American Chemical Society

Received: May 10, 2012

A

dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry

Article

Scheme 2. Interaction of Acetylenes with Ylides 1

Scheme 3. Formation λ5-Phosphinolines and Furans

ing ylides 8a and 8b because the heterocycle attached to the P center determines the tendency for electrophilic substitution. We expect in the case of 5a less and in case of 5b more tendency to electrophilic substitution as compared to the phenyl ring. These ylides 8a and 8b were not described previously in the literature, and Scheme 4 exhibits the synthetic pathways leading to them. The desired mixed ylides 8a and 8b were isolated in 80−95% yield as tetrafluoroborates. The study of the photochemical reactions (2 h in CH2Cl2) of ylide 8a with acetylenes reveals the data given in Scheme 5. In the photochemical reaction of ylide 8a with phenylacetylene, we isolated only the corresponding phosphinoline 9 (RPh) in 10% yield. The isolation of this product demonstrates the higher activity of benzene as compared the pyrazole ring in the electrophilic substitution step. In contrast, the photochemical reaction of the ylide 8a with 9-ethynylphenanthrene afforded only the corresponding furan 10 (R = C14H9) in 30% yield. The low yields are mostly due to the poor solubility of starting material in a CH2Cl2 as well as the enhanced decomposition of the ylide 8a to give the corresponding phosphonium salt [Ph2PyrP+CH2COPh] BF4− 11 (up to 70%).15 These results have to be compared with our previous experiments on the thiophene series 8c14 which led only to phosphininothiophenes. Our reactions of the ylide 8b with various acetylenes such as phenylacetylene, 3-ethynylthiophene, 1-ethynyl-4-methoxybenzene, and 9-ethynylphenanthrene afforded either the furans 12 and 13 (Scheme 6) (yields 40−50%) or a new heterocyclic system: the phosphininofurans 14 and 15 (yields 50−65%). It is interesting to note that the reaction of ylide 8b with phenylacetylene proceeds in seconds without UV irradiation. A comparison between the triphenyl-substituted (1), pyrazolyldiphenyl-substituted (8a), and thienyl-substituted (8c) ylides with the furyl-substituted ylide 8b shows the higher reactivity for the latter. The ylide 8b reacts vigorously in daylight and even in the dark with high yields. Thus, we found that interaction of benzoyl-substituted ylide 8b,c with acetylenes depends on the aryl moiety at the acetylene unit and can lead to the selective formation of furans (12 and 13, daylight; 16, with UV irradiation) or annelated phosphinines, phosphininothiophene and phosphininofurans (14 and 15, daylight; 17,14 with UV irradiation). p-Methoxyphenylacetylene in reaction with the ylide (8b) in the dark leads to formation also the furan (12) with the same yield. 9-Ethynylphenanthrene in reaction with ylide 8b in the dark affords two heterocyclic systems, furan (13) and phosphininofuran (18), with 30% and 40% yields, respectively (see Scheme 7). All mentioned reactions are accompanied by the formation of the corresponding phosphonium salts [Ph2HetP+CH2COPh]BF4−. The isolation of iodobenzene confirms that the C−I bond in the ylide is cleaved.

substitution than the phenyl ring. The present paper concerns the future development of this idea, using furyl and pyrazolyl derivatives, which are correspondingly more and less prone to undergo electrophilic substitution as compared with phenyl.

■

RESULTS AND DISCUSSION We chose to use furyldiphenylphosphine 5b and (pyrazolyl)diphenylphosphine 5a (Scheme 4) to prepare the correspondScheme 4. Preparation of the Ylides 8

B

dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry

Article

Scheme 5. Photochemical Reactions of Ylide 8a with Acetylenes

Scheme 6. Reactions of the Ylide 8b with Acetylenes

Scheme 7. Reaction of the Ylide 8b with 9-Ethynylphenanthrene in the Dark

°C. 1H NMR (CDCl3), δ: 3.71 (s, 3H), 6.43 (d, 2H, J = 12.4 Hz); 7.18 (dd, 1H, J = 2.0 Hz, J = 2.3 Hz); 7.43 (dd, 2H, J = 7.8 Hz, J = 7.5 Hz); 7.56 (dd, 1H, J = 7.3 Hz, J = 7.3 Hz); 7.64−7.69 (m, 4H); 7.71 (dd, 1H, J = 2.0 Hz, J = 1.5 Hz); 7.75−7.79 (m, 2H); 7.96 (ddd, 4H, J = 7.3 Hz, J = 14.1 Hz, J = 1.0 Hz); 8.31 (d, 2H, J = 7.3 Hz). 13C NMR (CDCl3), δ: 39.7 (d, JCP = 63.6 Hz); 40.9; 117.2 (d, JCP = 92.2 Hz); 120.7 (d, JCP = 106.9 Hz); 121.6 (d, JCP = 16.9 Hz); 129.0; 130.0; 130.5 (d, JCP = 13.9 Hz); 133.77 (d, JCP = 11.0 Hz); 134.82 (d, JCP = 5.1 Hz); 135.0; 135.5; 140.0 (d, JCP = 15.4 Hz); 191.9 (d, JCP = 5.9 Hz). 31P NMR (CDCl3), δ: 8.61. IR, ν̃ /cm−1: 1660 (CO), 730− 770, 1480 (Ar). Anal. Calcd for C24H22BrN2OP: C, 61.95; H, 4.77; N, 6.02. Found: C, 61.77; H, 4.76; N, 6.03. Furan-2-yl(2-oxo-2-phenylethyl)diphenylphosphonium Bromide (6b). Yield: 3.40 g (80%). Mp: 239−240 °C. 1H NMR (CDCl3), δ: 6.39 (d, 2H, J = 12.4 Hz); 6.77−6.79 (m, 1H); 7.51 (t, 2H, J = 7.4 Hz); 7.60−7.68 (m, 5H); 7.74−7.79 (m, 2H); 7.92 (m, 1H); 7.96− 8.02 (m, 4H); 8.14 (dd, 1H, J = 1.0 Hz, J = 3.8 Hz); 8.39 (d, 2H, J = 7.3 Hz). 13C NMR (CDCl3), δ: 38.5 (d, JCP = 65.1 Hz); 113.1 (d, JCP = 8.8 Hz); 117.6 (d, JCP = 94.4 Hz); 129.0; 130.0; 130.1 (d, JCP = 13.9 Hz); 130.8 (d, JCP = 19.8 Hz); 133.7 (d, JCP = 130.3 Hz); 133.9 (d, JCP = 11.7 Hz); 134.9; 135.0 (d, JCP = 1.5 Hz); 152.3 (d, JCP = 8.1 Hz); 191.8 (d, JCP = 5.9 Hz). 31P NMR (CDCl3), δ: 9.87. IR, ν̃/cm−1: 1660 (CO), 730−760, 1470 (Ar). Anal. Calcd for C24H20BrO2P: C, 64.18; H, 4.58. Found: C, 63.87; H, 4.47. General Procedure for Preparation of Phosphoranes (7a,b). A solution of 118 mg of sodium methylate (2.2 mmol) in 1 mL of dry methanol was added gradually to a solution of 2.15 mmol phosphonium salt 8 in 5 mL of dry methanol at 0 to +5 °C. The mixture was stirred for 1 h and then evaporated in vacuo, and the residue was dissolved in 10 mL of methylene chloride. The precipitate of sodium bromide was separated from the solution of ylides 9 by

The structures of all obtained compounds were confirmed by H, 13C, and 31P NMR spectroscopy (see the Supporting Information). 1

■

CONCLUSION Our investigations revealed that the products of the reactions between benzoyl-substituted phosphonium−iodonium ylides and arylacetylenes depend on the aryl moiety and the substituents on the phosphonium group. It can either lead to the selective formation of furans or to annelated phosphinolines and phosphininofurans.

■

EXPERIMENTAL SECTION

General Methods. The 1H, 31P, and 13C NMR spectra were recorded in CDCl3, CD2Cl2, and CD3CN with Me4Si as the internal standard. 1H NMR spectra were measured at 400 MHz and 13C NMR at 100 MHz. The IR spectra were measured in CCl4. The mass spectra were obtained on a quadrupole mass spectrometer (EI, 70 eV, direct inlet). The progress of the reactions and the purity after chromatographic separation were monitored by TLC on silica gel 60 plates. Chromatographic separation was carried out on columns with silica gel 60. General Procedure for Preparation of Phosphonium Salts (6a,b). Bromoacetophenone 1.57 g (7.9 mmol) was dissolved in 8 mL of dry acetonitrile, and 7.52 mmol phosphine was added. The mixture was stirred for 30 min, and the precipitate was filtered, washed with acetonitrile (3 × 5 mL) and diethyl ether (5 mL), and dried at room temperature. (1-Methyl-1H-pyrazol-5-yl)(2-oxo-2-phenylethyl)diphenylphosphonium Bromide (6a). Yield: 2.70 g (80%). Mp: 219 C

dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry

Article

filtration, washed on the filter with methylene chloride (3 × 10 mL). The residue was evaporated in vacuo. 1-[(1-Methyl-1H-pyrazol-5-yl)(diphenyl)phosphonio]-2-oxo-2phenylethanide (7a). Yield: 0.67 g (80%). Mp: 115−116 °C. 1H NMR (CDCl3), δ: 3.79 (s, 3H); 4.58 (d, 1H, J = 27.3 Hz); 6.24 (s, 1H); 7.36−7.38 (m, 3H); 7.60−7.75 (m, 11H); 7.90−7.92 (m, 2H). 13 C NMR (CDCl3), δ: 40.3, 47.7 (d, JCP = 113.4 Hz); 118.3 (d, JCP = 15.3 Hz); 126.5 (d, JCP = 95.1 Hz); 127.2; 128.3; 128.8 (d, JCP = 104.6 Hz); 129.8 (d, JCP = 13,2 Hz); 130.1; 132.8 (d, JCP = 10.2 Hz); 133.2; 138.9 (d, JCP = 13.1 Hz); 140.8 (d, JCP = 14.6 Hz); 180.2. 31P NMR (CDCl3), δ: 1.44. IR, ν̃/cm−1: 1590 (CO), 700−740, 1460 (Ar). Anal. Calcd for C24H21NOP: C, 74.99; H, 5.51; N, 7.29. Found: C, 75.26; H, 5.31; N, 7.05. 1-[Furan-2-yl(diphenyl)phosphonio]-2-oxo-2-phenylethanide (7b). Yield: 0,74 g (95%). Mp: 167−168 °C. 1H NMR (CD2Cl2), δ: 4.40 (d, 1H, J = 23.5 Hz); 6.63−6.64 (m, 1H); 7.21−7.22 (m, 1H); 7.39−7.40 (m, 3H); 7.40 (d, 1H, J = 1.8 Hz) 7.51−7.55 (m, 4H, J = 18.3 Hz); 7.61−7.65 (m, 2H); 7.76−7.83 (m, 5H); 7.92−7.95 (m, 2H). 13C NMR (CDCl3), δ: 47.8 (d, JCP = 117.8 Hz); 111.5 (d, JCP = 8.0 Hz); 124.8 (d, JCP = 18.3 Hz); 126.3 (d, JCP = 96.6 Hz); 127.0; 127.8; 128.8 (d, JCP = 13.2 Hz); 129.6; 132.2; 132.9 (d, JCP = 11.0 Hz); 140.7 (d, JCP = 14.6 Hz); 149.0 (d, JCP = 4.9 Hz); 185.5. 31P NMR (CDCl3), δ: 2.93. IR, ν̃/cm−1: 1590 (CO), 700−730, 1450 (Ar). Anal. Calcd for C24H19O2P: C, 77.83; H, 5.17. Found: C, 77.65; H, 5.25. General Procedure for Preparation of Phosphonium− Iodonium Ylides (8a,b). A solution of 1.3 mmol of diacetoxyiodobenzene in 3 mL of methanol was added to the solution of 1.3 mmol ylide 7 in 2 mL of methanol at 0−5 °C, and then 1.3 mmol of a solution of HBF4 (40%) was added at 0−5 °C. The mixture was stirred for 1 h, 10 mL of diethyl ether was added, and the mixture was stirred for 1 h. The precipitate was filtered and washed with diethyl ether. 1-[(1-Methyl-1H-pyrazol-5-yl)(diphenyl)phosphonio]-2-oxo-2phenyl-1-(phenyliodonio)ethanide tTetrafluoroborate (8a). Yield: 0,69 g (80%). Mp: 158 °C. 1H NMR (CD3CN), δ: 3.50 (s, 3H); 6.50 (dd, 1H, J = 2.0 Hz, J = 2.3 Hz); 7.20 (d, 2H, J = 7.8 Hz); 7.43 (dd, 2H, J = 7.9 Hz, J = 8.0 Hz); 7.51−7.57 (m, 3H); 7.61−7.68 (m, 11H); 7.70 (dd, 1H, J = 2.0 Hz, J = 1.5 Hz); 7.78−7.83 (m, 2H). 13C NMR (CD3CN), δ: 40.3; 120.4 (d, JCP = 17.5 Hz); 122.1 (d, JCP = 96.5 Hz); 125.8 (d, JCP = 108.3 Hz); 127.6; 128.6; 129.9 (d, JCP = 13.2 Hz); 130.8; 131.9; 132.6; 133.2 (d, JCP = 8.0 Hz); 133.2; 134.3; 138.8 (d, JCP = 8.1 Hz); 139.5 (d, JCP = 15.4 Hz); 192.1 (d, JCP = 6.6 Hz). 31P NMR (CD3CN), δ: 12.89. IR, ν̃/cm−1: 1600 (CO), 1080 (BF4−), 740−750, 1470 (Ar). Anal. Calcd for C30H26BF4IN2OP: C, 53.36; H, 3.88; N, 4.15. Found: C, C, 53.29; H, 3.93, N, 3.95. 1-[Furan-2-yl(diphenyl)phosphonio]-2-oxo-2-phenyl-1(phenyliodonio)ethanide Tetrafluoroborate (8b). Yield: 0,82 g (95%). Mp: 155 °C. 1H NMR(CD3CN), δ: 6.84−7.86 (m, 1H); 7.14−7.18 (m, 1H); 7.36−7.40 (m, 6H); 7.46−7.76 (m, 14H); 8.11− 8.14 (m., 1H). 13C NMR (CD3CN), δ: 113.8 (d, 8JCP = 8.8 Hz); 123.5 (d, JCP = 98.1 Hz); 128.9; 129.8; 129.9 (d, JCP = 19.0 Hz); 130.9 (d, JCP = 13.9 Hz); 131.9; 133.0; 133.4; 134.6 (d, JCP = 11.0 Hz); 135.5; 140.1 (d, JCP = 131.0 Hz); 140.1 (d, JCP = 6.6 Hz); 153.3 (d, JCP = 7.3 Hz); 192.9. 31P NMR (CD3CN), δ: 14.60. IR, ν̃/cm−1: 1540 (CO), 1070−1110 (BF4−), 740, 1470 (Ar). Anal. Calcd for C30H23BF4IO2P: C, 54.58; H, 3.51. Found: C, 54.81; H, 3.73. General Procedure for the Reaction of Ylides (8a) with Alkynes. The ylide (0.3 mmol) was added gradually to a solution of alkynes (0.9 mmol) in anhydrous dichloromethane. The reactions were irradiated in a quartz flask with a mercury lamp (366 nm) source under argon atmosphere. The progress of the reaction was monitored by TLC. After the end of the reaction, the mixtures were concentrated in vacuo. The residue was dissolved in a minimum of CH2Cl2 and chromatographed on silica gel. Benzene was used to elute phenylacetylene and PhI; the corresponding phosphinoline was eluted by using a CH2Cl2/MeOH mixture in a ratio of 200:1, the furan was eluted by using a CH2Cl2/CH3CN mixture in a ratio of 5:1. [1-(1-Methyl-1H-pyrazol-5-yl)-1,4-diphenyl-1λ5-phosphinolin-2yl](phenyl)methanone (9). Yield: 15 mg (10%). Red oil. 1H NMR(CDCl3), δ: 3.86 (s, 3H); 6.69 (dd, 1H, J = 2.0 Hz, J = 2.0

Hz); 7.17 (d, 1H, J = 33.1 Hz); 7.36 (d, 1H, J = 1.8 Hz); 7.34−7.44 (m, 11H); 7.53−7.57 (m, 3H); 7.62 (dd 1H, J = 2.0 Hz, J = 1.5 Hz); 7.64−7.67 (m, 2H); 7.98 (ddd, 2H, J = 6.9 Hz, J = 13.9 Hz, J = 1.6 Hz). 13C NMR (CDCl3), δ: 30.3 (d, JCP = 120.0 Hz); 39.8; 118.0 (d, JCP = 16.8 Hz); 124.9 (d, JCP = 11.0 Hz); 126.3 (d, JCP = 8.1 Hz); 126.5; 126.8 (d, JCP = 5.8 Hz); 127.6 (d, JCP = 94.4 Hz); 128.4 (d, JCP = 85.6 Hz); 128.4; 128.7; 129.0; 129.1; 129.1; 130.2 (d, JCP = 7.3 Hz); 132.4; 132.6; 133.0 (d, JCP = 99.5 Hz); 133.1; 133.4 (d, JCP = 11.7 Hz); 135.0 (d, JCP = 6.5 Hz); 138.5 (d, JCP = 14.6 Hz); 140.1; 190.3. 31P NMR (CDCl3), δ: −12.03. (1-Methyl-1H-pyrazol-5-yl)[5-(phenanthren-9-yl)-2-phenylfuran3-yl]diphenylphosphonium Tetrafluoroborate (10). Yield: 60 mg (30%). Colorless oil. 1H NMR(CD2Cl2), δ: 3.50 (s, 3H); 6.80 (dd, 1H, J = 2.2 Hz, J = 2.7 Hz); 6.82 (d, 1H, J = 3.9 Hz); 7.13−7.17 (m, 2H); 7.13−7.17 (m, 2H); 7.25−7.32 (m, 3H); 7.57−7.64 (m, 2H); 7.66−7.75 (m, 11H); 7.80−7.85 (m, 2H); 7.92 (dd, 1H, J = 8.0 Hz, J = 7.9 Hz); 8.08 (s, 1H); 8.20 (dd, 1H, J = 7.9 Hz, J = 1.1 Hz); 8.65 (d, 1H, J = 7.9 Hz); 8.74 (ddd, 1H, J = 7.5 Hz, J = 8.3 Hz, J = 1.4 Hz). 13C NMR (CD2Cl2), δ: 42.3; 98.9 (d, JCP = 114.0 Hz); 114.8 (d, JCP = 12.9 Hz); 118.5 (d, JCP = 96.0 Hz); 122.1 (d, JCP = 112.8 Hz); 123.3 (d, JCP = 18.5 Hz); 124.3; 125.1; 125.7; 126.8; 128.6; 129.0; 129.1 (d, JCP = 3.2 Hz); 129.80; 130.0; 130.3; 130.5; 130.9; 131.3; 132.3; 132.4; 132.5; 132.8 (d, JCP = 13.6 Hz); 132.9 (d, JCP = 4.0 Hz); 135.2 (d, JCP = 11.6 Hz); 138.0 (d, JCP = 2.8 Hz); 142.2 (d, JCP = 16.5 Hz); 158.5 (d, JCP = 15.7 Hz); 164.9 (d, 9JCP = 18.5 Hz). 31P NMR (CD2Cl2), δ: 2.49. IR, ν̃/cm−1: 1070 (BF4−), 700−760, 1470 (Ar). HRMS: calcd for C40H30N2OP (M+) m/z 585.2090, found 585.2077. General Procedure for the Reaction of Ylides (8b,c14) with Alkynes. The alkyne was added to a solution of ylide 8b,c (0.3 mmol) in anhydrous methylene chloride. The mixture was stirred under argon atmosphere. The progress of the reaction was monitored by TLC. After the end of the reaction, the mixture was concentrated in vacuo. The residue was dissolved in a minimum of CH2Cl2 and chromatographed on silica gel. Benzene was used to elute the residual alkynes and PhI; the corresponding phosphinoline was eluted by using a CH2Cl2/MeOH mixture in a ratio of 200:1, the furans were eluted by using a CH2Cl2/CH3CN mixture in a ratio of 5:1. 2,3-Dihydrofuran-2-yl[5-(4-methoxyphenyl)-2-phenylfuran-3-yl]diphenylphosphonium Tetrafluoroborate (12). Yield: 70 mg (40%). Colorless oil. 1H NMR (CDCl3), δ: 3.86 (s, 3H); 6.63 (d, 1H, J = 4.0 Hz); 6.76−6.77 (m, 1H.); 6.98 (d, 2H, J = 8.8 Hz); 7.13−7.17 (m, 2H); 7.22−7.23 (m, 2H); 7.26−7.30 (m, 1H); 7.34−7.35 (m, 1H); 7.68−7.78 (m, 10H); 7.82−7.86 (m, 2H); 8.01−8.02 (m, 1H). 13C NMR (CD2Cl2), δ: 57.0; 98.8 (d, JCP = 115.7 Hz); 109.0 (d, JCP =12.5 Hz); 114.6 (d, JCP = 9.6 Hz); 116.2; 118.5 (d, JCP = 97.6 Hz); 122.3; 127.8; 128.9; 129.8; 130.2; 132.3 (d, JCP = 13.7 Hz); 132.3; 132.6 (d, JCP = 20.5 Hz); 135.1 (d, JCP = 135.7 Hz); 135.3 (d, JCP = 11.6 Hz); 137.65 (d, JCP = 3.21 Hz); 155.5 (d, JCP = 8.0 Hz); 158.6 (d, JCP =15.3 Hz); 162.5; 164.0 (d, JCP =19.3 Hz). 31P NMR (CD2Cl2), δ: 3.39. IR, ν̃/cm−1: 1030−1100 (BF4−), 710−740, 1450 (Ar). HRMS: calcd for C33H26O3P (M+) m/z 501.1614, found 501.1611. Furan-2-yl[5-(phenanthren-9-yl)-2-phenylfuran-3-yl]diphenylphosphonium Tetrafluoroborate (13). Yield: 98 mg (50%). Colorless oil. 1H NMR (CD2Cl2), δ: 6.81 (m, 1H); 6.93 (d, 1H, J = 4.1 Hz); 7.22−7.26 (m, 2H); 7.37−7.40 (m, 4H); 7.70−7.95 (m, 14H); 8.04 (d, 1H, J = 7.9 Hz); 8.08−8.09 (m, 1H); 8.20 (s, 1H); 8.37 (dd, 1H, J = 8.1 Hz, J = 8.4 Hz); 8.77 (d, 1H, J = 8.4 Hz); 8.85 (d, 1H, J = 8.1 Hz). 13C NMR (CD2Cl2), δ: 97.8 (d, JCP = 115.6 Hz); 113.6 (d, JCP = 9.6 Hz); 114.1 (d, JCP = 12.5 Hz); 117.4 (d, JCP = 97.6 Hz); 123.3; 124.0; 124.9; 125.9; 127.8; 127.9; 128.0 (d, JCP = 4.1 Hz); 128.9; 129.0; 129.3; 129.3; 129.9 (d, JCP = 13.2 Hz); 131.3 (d, JCP = 14.0 Hz); 131.4 (d, JCP = 7.7 Hz); 131.5; 131.7; 131.9; 134.1 (d, JCP = 136.1 Hz); 134.3 (d, JCP = 11.6 Hz); 136.7 (d, JCP = 2.8 Hz); 154.5 (d, JCP = 8.0 Hz); 156.9 (d, JCP = 15.3 Hz); 164.3 (d, JCP = 18.8 Hz). 31P NMR (CD2Cl2), δ: 1.41. IR, ν̃/cm−1: 1070 (BF4−), 730−760, 1470 (Ar). HRMS: calcd for C40H28O2P (M+) m/z 571.1821, found 571.1817. Phenyl(4,7,7-triphenyl-7λ 5 -phosphinino[2,3-b]furan-6-yl)methanone (14). Yield: 71 mg (50%). Red oil. 1H NMR (CDCl3), δ: 6.51 (dd, 1H, J = 2.3 Hz, J = 2.2 Hz); 7.22−7.26 (m, 1H); 7.42 (d, 1H, D

dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry

■

J = 34.1 Hz); 7.35−7.39 (m, 2H); 7.42−7.47 (m, 3H); 7.46 (dd, 1H, J = 2.2 Hz, J = 2.3 Hz); 7.50−7.57 (m, 8H); 7.67−7.69 (m, 2H); 7.86 (dd, 4H, J = 7.6 Hz, J = 13.9 Hz). 13C NMR (CDCl3), δ: 78.9 (d, JCP = 103.9 Hz); 91.5 (d, JCP = 104.7 Hz); 107.0 (d, JCP = 2.9 Hz); 110.7 (d, JCP = 7.3 Hz); 125.8; 127.2 (d, JCP = 98.1 Hz); 127.6; 128.1; 128.3; 128.5 (d, JCP = 13.2 Hz); 128.7; 129.7; 131.6; 132.9 (d, arom., 2JCP = 11.7 Hz); 133.4 (d, JCP = 8.1 Hz); 138.1; 140.2 (d, JCP = 8.8 Hz); 141.2 (d, JCP = 13.2 Hz); 161.4 (d, JCP = 12.5 Hz); 191.6 (d, JCP = 5.9 Hz). 31P NMR (CDCl3), δ: 2.09. IR, ν̃/cm−1: 1520−1590 (CO), 710−740, 1470 (Ar). HRMS: calcd for C32H23O2P (M+) m/z 470.1436, found 470.1418. [7,7-Diphenyl-4-(thiophene-3-yl)-7λ5-phosphinino[2,3-b]furan-6yl](phenyl)methanone (15). Yield: 93 mg (65%). Red oil. 1H NMR (CD2Cl2), δ: 6.42 (dd, 1H, J = 2.0 Hz, J = 2.6 Hz); 7.15−7.19 (m, 2H); 7.42 (d, 1H, J = 36.2 Hz); 7.32−7.36 (m, 3H); 7.40 (dd, 1H, J = 3.43 Hz, J = 1.87 Hz); 7.41−7.49 (m, 7H); 7.51−7.54 (m, 2H); 7.72 (dddd, 4H, J = 6.7 Hz, J = 14.0 Hz, J = 1.4 Hz, J = 1.7 Hz). 13C NMR (CD2Cl2), δ: 80.1 (d, JCP = 104.0 Hz); 93.0 (d, JCP = 104.0 Hz); 103.8 (d, JCP = 4.4 Hz); 112.2 (d, JCP = 7.3 Hz); 119.9; 126.2; 128.3; 128.9 (d, JCP = 97.6 Hz); 129.7; 130.1; 130.1 (d, JCP = 13.0 Hz); 131.3; 133.3 (d, JCP = 3.2 Hz); 133.8 (d, JCP = 8.8 Hz); 134.45 (d, JCP = 11.6 Hz); 139.8; 141.9 (d, JCP = 8.8 Hz); 143.1 (d, JCP = 13.2 Hz); 162.9 (d, JCP = 12.9 Hz); 192.7 (d, JCP = 5.6 Hz) 31P NMR (CDCl3), δ: 1.54. IR, ν̃/ cm−1: 1520−1580 (CO), 710−760, 1470 (Ar). HRMS: calcd for C30H21O2PS (M+) m/z 476.0999, found 476.0985. [5-(Phenanthren-9-yl)-2-phenylfuran-3-yl](diphenyl)thiophene2-ylphosphonium Tetrafluoroborate (16). Yield: 142 mg (70%). Colorless oil (reaction with UV irradiation with a mercury lamp (366 nm)). 1H NMR (CD2Cl2), δ: 6.82 (d, 1H, J = 4.0 Hz); 7.18 (dd, 2H, J = 7.3 Hz, J = 8.1 Hz); 7.32−7.35 (m, 3H); 7.43−7.45 (m, 1H);7.66− 7.90 (m, 15H); 8.00 (d, 1H, J = 7.8 Hz); 8.15 (s, 1H); 8.22 (dt, 1H, J = 4.8 Hz, J = 1.3 Hz); 8.31 (dd, 1H, J = 8.1 Hz, J = 1.5 Hz); 8.74 (d, 1H, J = 8.3 Hz); 8.83 (d, 1H, J = 8.3 Hz). 13C NMR (CD2Cl2), δ: 99.1 (d, JCP = 114.1 Hz); 113.8 (d, JCP = 12.5 Hz); 116.6 (d, JCP = 98.8 Hz); 118.6 (d, JCP = 96.6 Hz); 122.7; 123.4; 124.3; 125.3; 127.3; 127.5; 128.3; 128.7; 129.3; 130.0; 130.7 (d, JCP = 13.9 Hz); 130.7 (d, JCP = 16.1 Hz); 130.9; 133.7 (d, JCP = 11.0 Hz); 136.0; 140.5 (d, JCP = 5.1 Hz); 143.0 (d, JCP = 11.0 Hz); 156.1 (d, JCP = 16.1 Hz); 163.1 (d, JCP = 17.6 Hz). 31P NMR (CD2Cl2), δ: 7.95. IR, ν̃/cm−1: 1070 (BF4−), 730−760, 1470 (Ar). HRMS: calcd for C40H28OPS (M+) m/z 587.1593, found 587.1593. Phenyl(4,7,7-triphenyl-7λ5-phosphinino[2,3-b]thiophene-6-yl)methanone (17). Yield: 44 mg (30%). Red oil (reaction with UV irradiation with a mercury lamp (366 nm)). 1H NMR (CD2Cl2), δ: 7.04 (dd, 1H, J = 5.3 Hz, J = 3.6 Hz); 7.10 (dd, 1H, J = 5.3 Hz, J = 2.8 Hz); 7.17 (d, 1H, J = 34.0 Hz); 7.24−7.28 (m, 1H); 7.34−7.38 (m, 2H); 7.40−7.43 (m, 3H); 7.50−7.60 (m, 8H); 7.62−7.64 (m, 2H); 7.82−7.87 (m, 4H). 13C NMR (CD2Cl2), δ: 78.5 (d, JCP = 103.4 Hz); 107.0 (d, JCP = 90.8 Hz); 113.5 (d, JCP = 8.1 Hz); 122.1 (d, JCP = 16.5 Hz); 127.1; 128.1 (d, JCP = 98.8 Hz); 128.6; 128.8; 129.1; 129.1 (d, JCP = 13.3 Hz); 129.1; 129.2 (d, JCP = 11.1 Hz); 130.2; 132.2 (d, JCP = 7.6 Hz); 132.3 (d, JCP = 3.2 Hz); 133.6 (d, JCP = 11.2 Hz); 141.2 (d, JCP = 9.3 Hz); 142.8; 154.2 (d, JCP = 8.0 Hz); 191.5 (d, JCP = 5.6 Hz) 31P NMR (CD2Cl2), δ: 1.97. MS, m/z: 486 [M]+, 409 [M − C6H5]+, 381 [M − PhCO]+, 183 [Ph2P − 2H]+. [4-(Phenanthren-9-yl)-7,7-diphenyl-7λ 5 -phosphinino[2,3-b]furan-6-yl](phenyl)methanone (18). Yield: 68 mg (40%). Red oil. 1H NMR (CD2Cl2), δ: 6.45 (dd, 1H, J = 2.2 Hz, J = 2.3 Hz); 7.23 (d, 1H, J = 36.4 Hz); 7.21 (dd, 1H, J = 2.4 Hz, J = 2.1 Hz); 7.22−7.25 (m, 3H); 7.42−7.58 (m, 12H); 7.66 (s, 1H); 7.76−7.87 (m, 6H); 8.61 (d, 1H, J = 8.3 Hz); 8.66 (d, 1H, J = 8.3 Hz). 13C NMR (CD2Cl2), δ: 80.1 (d, JCP = 104.0 Hz); 92.6 (d, JCP = 104.0 Hz); 107.2 (d, JCP = 1.6 Hz); 112.2 (d, JCP = 6.8 Hz); 124.1; 124.4; 127.9; 128.0; 128.; 128.7; 129.6; 129.7; 130.0; 130.2 (d, JCP = 13.6 Hz); 131.2 (d, JCP = 92.4 Hz); 131.2; 131.6; 133.4 (d, JCP = 3.3 Hz); 133.5; 133.9; 134.6 (d, JCP = 11.6 Hz); 135.7 (d, JCP = 8.1 Hz); 136.5; 139.6 (d, JCP = 7.7 Hz); 141.6 (d, JCP = 8.8 Hz); 143.5 (d, JCP = 13.7 Hz); 163.8; 192.4. 31P NMR (CD2Cl2), δ: 4.37. IR, ν̃/cm−1: 1520−1580 (CO), 700−800, 1470 (Ar). HRMS: calcd for C40H27O2P (M+) m/z 570.1743, found 570.1722.

Article

ASSOCIATED CONTENT

S Supporting Information *

1

H, 31P, and 13C NMR spectra of the new compounds 6−10, 12−16, and 18. This material is available free of charge via the Internet at http://pubs.acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We are grateful to the Russian Foundation for Basic Research (Project No. 11-03-00641) and the Division of Chemistry and Materials Science of the Russian Academy of Sciences (OChNM-1, and OChNM-9).

■

REFERENCES

(1) (a) Wittig, G. Acc. Chem. Res. 1974, 7, 6−14. (b) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863−927. (2) Taillefer, M.; Cristau, H. J. Top. Curr. Chem. 2003, 229, 41−73. (3) Neiland, O.; Vanag, G. Dokl. Acad. Nauk SSSR. 1964, 159, 373− 376. (4) Moriarty, R. M.; Prakash, I.; Prakash, O.; Freeman, W. A. J. Am. Chem. Soc. 1984, 106, 6082−6084. (5) Zhdankin, V. V.; Maydanovych, O.; Herschbach, J.; Bruno, J.; Matveeva, E. D.; Zefirov, N. S. J. Org. Chem. 2003, 68, 1018−1023. (6) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.; Takachev, V. V.; Zhdankin, V. V.; Aldoshin, S. M.; Zefirov, N. S. Russ. J. Org. Chem. 2003, 39, 536−541. (7) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.; Pavlova, A. S.; Zefirov, N. S. Russ. J. Org. Chem. 2007, 43, 201−206. (8) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.; Zefirov, N. S. Russ. Chem. Bull. 2008, 57, 400−405. (9) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.; Zefirov, N. S. Russ. Chem. Bull. 2008, 57, 2237−2239. (10) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.; Gleiter, R.; Zefirov, N. S. Eur. J. Org. Chem. 2009, 14, 2323−2327. (11) Nekipelova, T. D.; Kuzmin, V. A.; Matveeva, E. D.; Gleiter, R.; Zefirov, N. S. J. Phys. Org. Chem. 2012, DOI: 10.1002/poc.2972. (12) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.; Borisenko, A. A.; Gleiter, R.; Zefirov, N. S. J. Org. Chem. 2009, 74, 9428−9432. (13) Matveeva, E. D.; Gleiter, R.; Zefirov, N. S. Russ. Chem. Bull. 2010, 59, 488. (14) Matveeva, E. D.; Podrugina, T. A.; Taranova, M. A.; Borisenko, A. A.; Mironov, A. V.; Gleiter, R.; Zefirov, N. S. J. Org. Chem. 2011, 76, 566−572. (15) The decomposition of ylides to give the corresponding phosphonium salt is the common phenomenon, which we have observed in many different related photochemical processes. This reaction is under careful investigation, using deuterium labeling, because the source of two hydrogens is not absolutely clear yet.

E

dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX